CN105347516A - Device for treating high-concentration pharmaceutical wastewater through electric power assisted microbial enhanced degradation and method for treating pharmaceutical wastewater - Google Patents
Device for treating high-concentration pharmaceutical wastewater through electric power assisted microbial enhanced degradation and method for treating pharmaceutical wastewater Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/341—Consortia of bacteria
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/342—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/026—Treating water for medical or cosmetic purposes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
- C02F2203/004—Apparatus and plants for the biological treatment of water, waste water or sewage comprising a selector reactor for promoting floc-forming or other bacteria
Abstract
The invention provides a device for treating high-concentration pharmaceutical wastewater through electric power assisted microbial enhanced degradation and a method for treating the pharmaceutical wastewater, relates to a pharmaceutical wastewater treatment device and a pharmaceutical wastewater treatment method adopting the device and aims to solve the technical problems of low toxicity removal rate and poor COD (chemical oxygen demand) removal capacity of a conventional high-concentration pharmaceutical wastewater treatment method. The device comprises a water inlet, a water outlet, a tank body, a top cover, water quality monitoring ports, organic glass sheets, carbon fiber brushes, titanium wires, a gas collecting pipe, a wet gas flow meter, a water seal tank, a sludge deposit hopper and a sludge drain port. The method comprises steps as follows: step one, sludge is sieved by a screen, pharmaceutical wastewater is added to the sludge, NaH2PO3 and NH4Cl are added, acclimatization is performed for 2 weeks, and a mixture after acclimatization is added to each isolation chamber of the pharmaceutical wastewater treatment device; step two, the titanium wires are connected with a transformer, the device operates in a sequencing batch type mode, then the operating mode is changed into a continuous water feeding mode, water is discharged from the water outlet, and the water treatment process is finished. The device and the method are applied to the field of sewage treatment.
Description
Technical field
The present invention relates to a kind of pharmacy wastewater treatment device and utilize the method for this device Pharmaceutical Wastewater Treatment.
Background technology
The pollution problem of water resources exists always, has threatened the Sustainable development of entire society, and the improvement of water pollutions must be brought into schedule.According to Chinese Ministry of Environmental Protection's statistics, within 2012, national wastewater emission amount is 684.3 hundred million tons, reach over the years, only discharged volume of industrial waste water just accounts for 32.4%, and pharmaceutical industry is as the pillar industry of China's industry, and its discharge of wastewater accounts for the overwhelming majority of discharged volume of industrial waste water.Because current pharmaceutical industry production technique raw material availability is low, refinement purity is low, cause residual a large amount of high toxicity, hardly degraded organic substance in pharmacy waste water, serious pollution will certainly be caused to environment.The existence of the toxicant serious harm aquatic animals and plants in pharmacy waste water, some is bacteria growing inhibiting even, causes water body self-purification ability to weaken, and harm is aggravated.Its specific features is as follows: water-quality constituents is complicated, Pollutants in Wastewater matter content is high, COD value is high, hazardous and noxious substances is many, bio-refractory material is many, salt content is high, colourity is very high, high-concentration waste mother liquor generation large (150 ~ 850m3/t product).Pharmacy waste water has stronger bio-toxicity and bio-refractory, and its long-term existence, in environment, will cause in environment and occur resistant gene, and therefore, pharmacy waste water must effectively be processed.
Current pharmacy waste water mainly adopts Biochemical method to be main, but biological treatment is weak to pharmacy waste water toxicity removal ability, cause technique to remove COD, ammonia nitrogen ability declines, and in waste water, hard-degraded substance is more, can penetrate biological treatment and enter water body.In addition, conventional biological treatment method can not provide the redox potential of degradation of contaminant, complex compound in waste water in water through a series of biochemical action, react each other, generation degradation property is poor, the material that toxicity is large, and energy prolonged stay is in water, cause permanent harm, must seek a kind of can the novel process of efficient degradation pharmacy waste water toxic material.Along with promulgation and the enforcement of " emission standard of pharmaceutical industry pollutent ", at present conventional pharmacy wastewater treatment technology is also faced with the problem that the not up to standard and technique of water outlet needs upgrading, and therefore, rationally pharmaceutical wastewater treatment process is extremely urgent efficiently in development.
Summary of the invention
The present invention is the technical problem of the low and COD removal ability difference of the method wastewater toxicity clearance in order to solve existing process high concentration medical wastewater; and solve current microorganism electricity subsystem in due to the technical problem that catalyzer cost is higher, unreasonable this technique caused of reactor configuration is difficult to large-scale development, provide a kind of method that electricity assists microbial augmentation degrading high concentration pharmacy wastewater treatment device and Pharmaceutical Wastewater Treatment.
The auxiliary microbial augmentation degrading high concentration pharmacy wastewater treatment device of the present invention's electricity comprises water-in, water outlet, casing, top cover, water quality monitoring (WQM) mouth, poly (methyl methacrylate) plate, carbon fiber brush, titanium silk thread, effuser, wet test meter, flashback tank, deposition bucket and mud discharging mouth, described casing comprises eight compartments, is respectively the first compartment, second compartment, 3rd compartment, 4th compartment, 5th compartment, 6th compartment, 7th compartment and the 8th compartment, separated by dividing plate between adjacent compartment, dividing plate lower end between first compartment and the second compartment is provided with a linked hole, dividing plate upper end between second compartment and the 3rd compartment is provided with a linked hole, dividing plate lower end between 3rd compartment and the 4th compartment is provided with a linked hole, dividing plate upper end between 4th compartment and the 5th compartment is provided with a linked hole, dividing plate lower end between 5th compartment and the 6th compartment is provided with a linked hole, dividing plate upper end between 6th compartment and the 7th compartment is provided with a linked hole, and the dividing plate lower end between the 7th compartment and the 8th compartment is provided with a linked hole,
The upper end that the left side of described casing is positioned at outside the first compartment is provided with water-in, and the upper end that the right side of casing is positioned at outside the 8th compartment is provided with water outlet, and cabinet front and rear side are positioned at outside each compartment and are equipped with water quality monitoring (WQM) mouth;
The top of each compartment is equipped with poly (methyl methacrylate) plate, the lower surface of each poly (methyl methacrylate) plate is all parallel is fixed with five carbon fiber brush groups, equidistantly on casing fore-and-aft direction in each carbon fiber brush group be arranged with 4 carbon fiber brushes, the center of each carbon fiber brush is provided with titanium silk thread, titanium silk thread is exposed to the upper surface of poly (methyl methacrylate) plate through poly (methyl methacrylate) plate, and carbon fiber brush relies on titanium silk thread to be fixed on poly (methyl methacrylate) plate;
Three carbon fiber brush groups in five carbon fiber brush groups are as negative electrode, two carbon fiber brush groups are as anode, negative electrode and positive electrode is arrangement alternately, the titanium silk thread that each carbon fiber brush group as negative electrode is exposed to poly (methyl methacrylate) plate upper surface is all connected with the negative pole of transformer by wire, and the titanium silk thread that each carbon fiber brush group as anode is exposed to poly (methyl methacrylate) plate upper surface is all connected with the positive pole of transformer by wire;
Top cover is provided with above described casing, leave distance between top cover and poly (methyl methacrylate) plate, top cover is provided with effuser, and wet test meter is connected by water-sealed drainage bottle is airtight with effuser, the bottom of each compartment is equipped with deposition bucket, is equipped with mud discharging mouth bottom each deposition bucket.
Further, the water quality monitoring (WQM) mouth outside each compartment is 2 ~ 4, and the upper and lower be arranged at respectively outside each compartment from top to bottom arranges in turn.
Further, each carbon fiber brush is cylindric, and diameter is 2 ~ 4cm.
Further, each carbon fiber brush group is arranged in parallel on casing left and right directions, and dislocation arrangement between each carbon fiber brush group, make 3 of arbitrary neighborhood carbon fiber scopiforms become equilateral triangle, the distance between any two carbon fiber brushes is 4cm.
Further, the gap high vacuum silicone grease between described titanium silk thread and poly (methyl methacrylate) plate seals.
Further, the inclination angle of described deposition bucket sidewall is 60 degree.
Further, the low 5cm of height of aspect ratio second compartment of the space bar upper end linked hole of the 4th compartment and the 5th compartment and the space bar upper end linked hole of the 3rd compartment, the low 5cm of height of aspect ratio the 4th compartment of the space bar upper end linked hole of the 6th compartment and the 7th compartment and the space bar upper end linked hole of the 5th compartment.
Utilize above-mentioned electricity to assist the method for microbial augmentation degrading high concentration pharmacy wastewater treatment device Pharmaceutical Wastewater Treatment, carry out according to the following steps:
One, pharmaceutical factory sewage works second pond returned sluge is crossed 10 eye mesh screens and remove macrobead thing, then in mud, add fresh pharmacy waste water, and add NaH
2pO
3and NH
4cl is in mud and pharmacy waste water mixture, the mass ratio of COD:N:P is made to be 200:5:1, continuous domestication two weeks, then put into by the mixture after domestication in each compartment of the auxiliary microbial augmentation degrading high concentration pharmacy wastewater treatment device of electricity, inoculum size is 2/3 of each compartment useful volume;
Two, titanium silk thread is connected with transformer, transformer voltage is 0.7 ~ 1.2V, temperature of reaction is 25 ~ 35 DEG C, pH value 6 ~ 8, first run under sequence batch (pattern, when electricity assists the electric current between microbial augmentation degrading high concentration pharmacy wastewater treatment device inner cathode and anode to be greater than 25mA, when external wet test meter has monitored obvious gas output simultaneously, now carbon fiber brush surface biofilm success, operation scheme is changed into continuum micromeehanics pattern, arranging hydraulic detention time is 8 ~ 12h, ensure that the flow velocity that in casing, each compartment current rises or declines is 1 ~ 1.5m/h, water outlet water outlet, namely water treatment procedure is completed.
Sequence batch (pattern is that reactor reacts by water inlet, drainage period, and each cycle comprises into water, reaction, draining three steps; Continuum micromeehanics pattern refers to that waste water constantly entered and outflow reactor along with the time always, and the flow field in reactor is consistent with the exchange of material in time.
In step one, sludge concentration is 4 ~ 6g/L, and described sludge concentration refers to the concentration of living microorganism in mud.
In step one, the COD value of fresh pharmacy waste water is 2500 ~ 4000mg/L.
Principle of the present invention:
The auxiliary microbial augmentation degrading high concentration pharmacy wastewater treatment device of the present invention's electricity, effective volume 500L, it comprises eight identical compartments, be communicated with by boring a hole up and down between compartment, flow process reaches baffling effect, the water surface elevation of each compartment is determined by the height of perforation upper between two compartments, the effect of successively decrease successively along water (flow) direction 5cm, arrival plug-flow.Each compartment is an independently microorganism electric catalyticing system, negative electrode and anode material all adopt cylindric carbon fiber brush, central conductor is that titanium silk is made, vertical range between anode and cathode carbon fiber brush is 4cm, equilateral triangle anode and cathode is adopted to intersect, arrange that carbon fiber brush is arranged vertically, to reach best electrode surface area utilization ratio.Flow shear can make the microbial film of electrode surface upgrade comparatively fast simultaneously, and mass transfer effect is obvious.Eight compartments share an effuser, are connected with wet test meter.
The present invention adopts multi-group electrode to coexist in a compartment, in tandem in fluidised form, with there is excellent conductive performance and compared with the carbon fiber brush of bigger serface for anode and cathode material, according to needing target contaminant species to be processed in waste water, by changing impressed voltage, certain redox potential is provided near anode and cathode, under the katalysis of biting electric microorganism, by the electron transmission of external circuit to the antimicrobial surface of pollution degradation material, break the reaction energy barrier needed for microbiological deterioration pollution substance, improve electron transfer rate simultaneously, accelerate reaction process, thus the pollution in waste water can be made efficiently to remove, wastewater toxicity significantly reduces.
Apparatus of the present invention adopt multiple individual compartment series operation, and in each compartment, multi-group electrode is in parallel.Equilateral triangle arrangement between each carbon fiber brush, the effective use angle of electrode reaches 240 °.
The auxiliary microorganism reactor of apparatus of the present invention electricity starts, operational process adopts actual high concentration medical wastewater as substrate, and treatment scale reaches pilot scale level.
Beneficial effect of the present invention:
1, in apparatus of the present invention, current all present baffling form in the horizontal direction and the vertical direction, and water movement has irregularity, avoid the drawback that short stream easily appears in conventional reactor.
2, higher in apparatus of the present invention upper Flow Velocity is on the one hand for the microbial film of electrode surface provides larger shearing force, accelerate the biomembranous update of electrode surface, make biological membranous layer thinner, pollution substance is transferred to distance needed for microbial film inside from aqueous phase to be shortened greatly, reaction rate accelerates; Pollution substance distributes more even in aqueous phase on the other hand, and mass-transfer efficiency is very fast.
3, apparatus of the present invention, in the high concentration medical wastewater that can process as required, the different properties of pollution substance changes impressed voltage and negative electrode, anode electrode current potential, for microorganism provides pollution degradation material necessary redox potential, breaks reaction energy barrier.
4, the electrode materials loaded in apparatus of the present invention is carbon fiber brush, and cost reduces greatly than cathode material costs such as noble metal platinums in the past, and can according to organic waste water toxicity and concentration determination number of electrodes.
5, the spread pattern of apparatus of the present invention anode and cathode is equilateral triangle, the effective use angle of electrode being positioned at relative intermediate position can be made to reach 240 °, the efficiency utilization specific surface area of electrode and the useful space of reactor.Current the present invention has realized trying out in high concentration medical wastewater, waste water COD clearance is high, toxicant in water inlet is after device process of the present invention, through technical evaluation such as GC-MS/MS, major part toxicant is degraded to small organic molecule, lack of toxicity or weaken, treatment effect efficient stable, the industrial prospect of apparatus of the present invention is good.
Accompanying drawing explanation
Fig. 1 is the structural representation of apparatus of the present invention;
Fig. 2 is the plan structure schematic diagram of apparatus of the present invention;
Fig. 3 be in test 1 pharmacy wastewater treatment device to the removal effect figure of pharmacy waste water COD;
Fig. 4 be in test 1 pharmacy wastewater treatment device to the removal effect figure of pharmacy waste water total nitrogen;
Fig. 5 is the removal effect of pharmacy wastewater treatment device to benzothiazole in pharmacy waste water;
Fig. 6 is the removal effect of pharmacy wastewater treatment device to indoles in pharmacy waste water;
Fig. 7 is the removal effect of pharmacy wastewater treatment device to quinoline in pharmacy waste water;
Fig. 8 is the removal effect of pharmacy wastewater treatment device to pyridine in pharmacy waste water;
Fig. 9 is the removal effect of pharmacy wastewater treatment device to pharmacy waste water comprehensive toxicity;
Figure 10 is the positive electrode surface scan electromicroscopic photograph of pharmacy wastewater treatment device;
Figure 11 is the cathode electrode surface stereoscan photograph of pharmacy wastewater treatment device;
Figure 12 is the cluster analysis figure of the microflora of pharmacy wastewater treatment device Anodic and negative electrode.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: composition graphs 1 and Fig. 2 illustrate present embodiment, the auxiliary microbial augmentation degrading high concentration pharmacy wastewater treatment device of present embodiment electricity comprises water-in 1, water outlet 2, casing 3, top cover 4, water quality monitoring (WQM) mouth 5, poly (methyl methacrylate) plate 6, carbon fiber brush 8, titanium silk thread 9, effuser 7, wet test meter 10, water-sealed drainage bottle 11, deposition bucket 12 and mud discharging mouth 13, described casing 3 comprises eight compartments, is respectively the first compartment 3-1, second compartment 3-2, 3rd compartment 3-3, 4th compartment 3-4, 5th compartment 3-5, 6th compartment 3-6, 7th compartment 3-7 and the 8th compartment 3-8, separated by dividing plate between adjacent compartment, dividing plate lower end between first compartment 3-1 and the second compartment 3-2 is provided with a linked hole, dividing plate upper end between second compartment 3-2 and the 3rd compartment 3-3 is provided with a linked hole, dividing plate lower end between 3rd compartment 3-3 and the 4th compartment 3-4 is provided with a linked hole, dividing plate upper end between 4th compartment 3-4 and the 5th compartment 3-5 is provided with a linked hole, dividing plate lower end between 5th compartment 3-5 and the 6th compartment 3-6 is provided with a linked hole, dividing plate upper end between 6th compartment 3-6 and the 7th compartment 3-7 is provided with a linked hole, and the dividing plate lower end between the 7th compartment 3-7 and the 8th compartment 3-8 is provided with a linked hole,
The upper end that the left side of described casing 3 is positioned at outside the first compartment 3-1 is provided with water-in 1, and the upper end that the right side of casing 3 is positioned at outside the 8th compartment 3-8 is provided with water outlet 2, is positioned at outside each compartment is equipped with water quality monitoring (WQM) mouth 5 on front side of casing 3 with rear side;
The top of each compartment is equipped with poly (methyl methacrylate) plate 6, the lower surface of each poly (methyl methacrylate) plate is all parallel is fixed with five carbon fiber brush groups 15, equidistantly on casing fore-and-aft direction in each carbon fiber brush group 15 be arranged with 4 carbon fiber brushes 8, the center of each carbon fiber brush 8 is provided with titanium silk thread 9, and titanium silk thread 9 is exposed to the upper surface of poly (methyl methacrylate) plate 6 through poly (methyl methacrylate) plate 6;
Three carbon fiber brush groups in five carbon fiber brush groups are as negative electrode, two carbon fiber brush groups are as anode, negative electrode and positive electrode is arrangement alternately, the titanium silk thread that each carbon fiber brush group as negative electrode is exposed to poly (methyl methacrylate) plate upper surface is all connected with the negative pole of transformer by wire, and the titanium silk thread that each carbon fiber brush group as anode is exposed to poly (methyl methacrylate) plate upper surface is all connected with the positive pole of transformer by wire;
Top cover 4 is provided with above described casing 3, leave distance between top cover 4 and poly (methyl methacrylate) plate 6, top cover 4 is provided with effuser 7, and wet test meter 10 is connected by water-sealed drainage bottle 11 is airtight with effuser 7, the bottom of each compartment is equipped with deposition bucket 12, is equipped with mud discharging mouth 13 bottom each deposition bucket.
The principle of present embodiment: present embodiment adopts multiple independent case body series operation, in each independent case body, multi-group electrode is in parallel, to achieve between electrode and not only connects but also spatial distribution in parallel, weaken the pressure drop between electrode.Between each carbon fiber brush, the arrangement of equilateral triangle also achieves the at utmost utilization of space reactor, shortens the path of proton and electron transmission between electrode, improves speed of reaction.
Traditional anaerobic treatment and microorganism electrochemical process means combine by microorganism electricity ancillary technique, what be attached to electrode surface bites electric microorganism with organic substance in waste water for electron donor, while oxidation of organic compounds, transfer protons and electronics outside born of the same parents, proton arrives negative electrode by electrolytic solution, and electronics arrives negative electrode through anode and external circuit, applying electrical potential auxiliary under, proton becomes hydrogen with electronics in cathode junction symphysis, is clean energy by the chemical energy in organic substrates.Compared with general treatment technology, microorganism electricity ancillary technique is applicable to process high density, used water difficult to degradate, can carry out effective detoxification, reduce the processing cost of pharmacy waste water greatly to pharmacy waste water.
Embodiment two: present embodiment and embodiment one unlike: the water quality monitoring (WQM) mouth outside each compartment is 2 ~ 4, is arranged at the upper and lower outside each compartment respectively, from top to bottom arranges in turn.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: each carbon fiber brush 8 is in cylindric, and diameter is 2 ~ 4cm.Other is identical with embodiment one or two.
Be provided with titanium silk thread at the center of carbon fiber brush 8, effect is fixed carbon fiber brush, and titanium silk thread also has conduction and etch-proof effect in addition.
Embodiment four: one of present embodiment and embodiment one to three unlike: each carbon fiber brush group 15 is arranged in parallel on casing 3 left and right directions, dislocation arrangement between each carbon fiber brush group, make 3 of arbitrary neighborhood carbon fiber scopiforms become equilateral triangle, the distance between any two carbon fiber brushes is 4cm.Other is identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: the gap high vacuum silicone grease between described titanium silk thread 9 and poly (methyl methacrylate) plate 6 seals.Other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the inclination angle of described deposition bucket 12 sidewall is 60 degree.Other is identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six are unlike the low 5cm of height of the aspect ratio second compartment 3-2 of the space bar upper end linked hole of the 4th compartment 3-4 and the 5th compartment 3-5 and the space bar upper end linked hole of the 3rd compartment 3-3, the low 5cm of height of aspect ratio the 4th compartment 3-4 of the space bar upper end linked hole of the 6th compartment 3-6 and the 7th compartment 3-7 and the space bar upper end linked hole of the 5th compartment 3-5.Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment utilizes the method for the auxiliary microbial augmentation degrading high concentration pharmacy wastewater treatment device Pharmaceutical Wastewater Treatment of electricity, carries out according to the following steps:
One, pharmaceutical factory sewage works second pond returned sluge is crossed 10 eye mesh screens and remove macrobead thing, then in mud, add fresh pharmacy waste water, and add NaH
2pO
3and NH
4cl is in mud and pharmacy waste water mixture, the mass ratio of COD:N:P is made to be 200:5:1, continuous domestication two weeks, then put into by the mixture after domestication in each compartment of the auxiliary microbial augmentation degrading high concentration pharmacy wastewater treatment device of electricity, inoculum size is 2/3 of each compartment useful volume;
Two, titanium silk thread is connected with transformer, transformer voltage is 0.7 ~ 1.2V, temperature of reaction is 25 ~ 35 DEG C, pH value 6 ~ 8, first run under sequence batch (pattern, when electricity assists the electric current between microbial augmentation degrading high concentration pharmacy wastewater treatment device inner cathode and anode to be greater than 25mA, when external wet test meter has monitored obvious gas output simultaneously, now carbon fiber brush surface biofilm success, operation scheme is changed into continuum micromeehanics pattern, arranging hydraulic detention time is 8 ~ 12h, ensure that the flow velocity that in casing, each compartment current rises or declines is 1 ~ 1.5m/h, water outlet water outlet, namely water treatment procedure is completed.
Embodiment nine: present embodiment and embodiment eight unlike: in step one, sludge concentration is 4 ~ 6g/L, and described sludge concentration refers to the concentration of living microorganism in mud.Other is identical with embodiment eight.
Embodiment ten: present embodiment and embodiment eight or nine unlike: in step one, the COD value of fresh pharmacy waste water is 2500 ~ 4000mg/L.Other is identical with embodiment eight or nine.
For verifying that beneficial effect of the present invention carries out following test:
Test 1:
This test utilizes the method for the auxiliary microbial augmentation degrading high concentration pharmacy wastewater treatment device Pharmaceutical Wastewater Treatment of electricity, carries out according to the following steps:
One, pharmaceutical factory sewage works second pond returned sluge is crossed 10 eye mesh screens and remove macrobead thing, then in mud, add fresh pharmacy waste water, and add NaH
2pO
3and NH
4cl is in mud and pharmacy waste water mixture, the mass ratio of COD:N:P is made to be 200:5:1, continuous domestication two weeks, then put into by the mixture after domestication in each compartment of the auxiliary microbial augmentation degrading high concentration pharmacy wastewater treatment device of electricity, inoculum size is 2/3 of each compartment useful volume;
Two, titanium silk thread is connected with transformer, transformer voltage is 1V, temperature of reaction is 30 DEG C, pH value 7, first run under sequence batch (pattern, when electricity assists the electric current between microbial augmentation degrading high concentration pharmacy wastewater treatment device inner cathode and anode to be greater than 25mA, when external wet test meter has monitored obvious gas output simultaneously, now carbon fiber brush surface biofilm success, operation scheme is changed into continuum micromeehanics pattern, arranging hydraulic detention time is 10h, ensure that the flow velocity that in casing, each compartment current rises or declines is 1.5m/h, water outlet water outlet, namely water treatment procedure is completed.
Test effect is as follows:
(1) pharmacy wastewater treatment device device is to the removal effect of pharmacy waste water COD and total nitrogen
Inlet COD concentration greatly about about 4000mg/L, as shown in Figure 3, in Fig. 3-◆-represent water inlet ,-△-expressions water outlet ,-×-expression clearance, when system stable operation, COD is about about 1200mg/L in system water outlet, and effluent quality is relatively stable.The raw plain waste water COD clearance of system counter is about about 70%, and in system, the removal of most COD comes from the acting in conjunction of microorganism and electrode in auxiliary microflora.
In pharmacy waste water, the existence form of total nitrogen has ammonia nitrogen, nitric nitrogen and nitrite nitrogen and organism nitrogen, and the nitrogen of various form is all present in this system, and can transform between the form of nitrogen, as the carbonnitrogen bond fracture in organism, organonitrogen can change into other forms of nitrogen.Some meeting of the removal of total nitrogen be consumed along with microbial growth, some will be consumed under the effect of microorganism and electrode, apparatus of the present invention to the removal situation of total nitrogen in pharmacy waste water as shown in Figure 4, in Fig. 4-◆-represent water inlet,-△-expression water outlet ,-×-represent clearance.In water inlet, the concentration of TN is about 180mg/L, and aqueous concentration is substantially between 120 ~ 140mg/L, and nitrogen removal rate is about about 30%.Mainly give the credit to ammonia nitrogen to be oxidized at anode, and nitric nitrogen and nitrite nitrogen are reduced at negative electrode.Negative electrode is as an electron source simultaneously, and denitrification also can occur at negative electrode.Such anode and cathode microbial have the process participating in denitrogenation.Meanwhile, because system sampling mouth may cause system to have a small amount of oxygen to enter, cause ammonia nitrogen to the conversion of nitric nitrogen.
(2) apparatus of the present invention are to the removal effect of toxic substance in pharmacy waste water
In pharmacy waste water, organic pollutant is very harmful, if do not carry out effective process can have great restraining effect to microorganism.When benzothiazole concentration is 7mg/L, ammonia oxidation efficiency can be made to reduce by 50%, when concentration reaches 54mg/L, ammonia oxidation etc. can be suppressed completely.Quinoline etc. be toxicity ratio benzothiazole the larger antibiotic agents of toxicity.
The mass concentration of benzothiazole, pyridine is 50mg/L, and indoles, quinoline are 100mg/L, records the removal situation of four kinds of materials after operation for some time steady in a long-term.As viewed in figures 5-8, in Fig. 5-8-◆-represent water inlet ,-△-expressions water outlet ,-×-expression clearance.Fig. 5 is the removal effect of pharmacy wastewater treatment device to benzothiazole in pharmacy waste water, Fig. 6 is the removal effect of pharmacy wastewater treatment device to indoles in pharmacy waste water, Fig. 7 is the removal effect of pharmacy wastewater treatment device to quinoline in pharmacy waste water, Fig. 8 is the removal effect of pharmacy wastewater treatment device to pyridine in pharmacy waste water, and microorganism electric catalyticing system can realize stable repetition degradation characteristic to four kinds of materials instead of accidental result.At acidication 8h, after microorganism electrocatalysis 24h, the removal of contrive equipment to benzothiazole and indoles reaches 90% and 70% respectively, and lower to the degraded of quinoline and pyridine, clearance is only 20% and about 50%.
In this individual system, the organic clearance of the five-ring such as benzothiazole and indoles is greater than the six-ring such as quinoline and pyridine organism, reason may with the structure of material and charge property relevant.Indoles is 9 electronics 10 π-electron systems, and heterocycle conjugated system makes the cloud density in nitrogen heterocyclic ring increase, and is easily subject to the attack of electrophilic reagent.And quinoline and pyridine are hexa-member heterocycle, character is comparatively stable, and it is higher that ring texture breaks the energy needed in the process of ring.When the similar of pollution substance, can show similar degradation characteristic, the enzyme that they utilize when microorganism vivo degradation is similar or identical, so induce the enzyme of generation to utilize each other in the process of degraded.
(3) contrive equipment is to the removal effect of pharmacy waste water comprehensive toxicity
Pharmacy waste water has restraining effect to microorganism, pharmacy wastewater treatment device to the removal effect of pharmacy waste water comprehensive toxicity as shown in Figure 9, in Fig. 9-◆-represent water inlet ,-▲-represent water outlet.As can be seen from Figure 9, the toxicity of waste water to photogenic bacterium through apparatus of the present invention process decreases.When not diluting when intaking, the toxicity inhibition rate of former water to photogenic bacterium is about 99%, and the toxicity inhibition rate of water outlet to photogenic bacterium after apparatus of the present invention process is about 65%.
(4) microorganism scanning electron microscopic observation in contrive equipment
For having more detailed understanding to the microorganism structure of electrode surface, in experimentation, take off fritter electrode materials with the instrument of sterilization and carry out scanning electron microscopic observation, Figure 10 is the positive electrode surface scan electromicroscopic photograph of device, and Figure 11 is the cathode electrode surface stereoscan photograph of device.As can be seen from Figure 10 and 11, electrode surface has a large amount of microorganisms, and bacterium is mainly in shaft-like and spherical.And the thickness of microbial film is not very large, microorganism can touch electrode substantially, main is all electrochemical activity bacterium, substantially increase the ability of the transmission electronics of microorganism like this, additionally reduce the competition between electrochemical activity bacterium and other anaerobic bacteria floras, these are different from adopting separately the Flora distribution of the auxiliary microbiological processes of electricity.
(5) in contrive equipment, biological community structure is resolved
The steady running of the auxiliary microflora of electricity relies on the acting in conjunction of anode and cathode microbial.As shown in figure 12, as can be seen from the cluster analysis figure of microflora, being similar in kind of anode and cathode microbial, relative abundance is variant for the cluster analysis figure of the microflora of anode and negative electrode.
The topmost electrochemical activity bacterium of electrode comprises Bacteroidetes and Proteobacteria (also comprising Cyanobacteria, Armatimonadetes, Deinococcus etc.), the two is all larger in the abundance of anode and cathode, at present confirmed electrode activity bacterium Shewanellaoneidensis and Geobactersulfurreducens, this two kinds of outside conveying electronics of bacterium very competent.In the level of door, the two all belongs to Proteobacteria.Shewanellaoneidensis and Geobactersulfurreducens can by the special construction of cell surface by electron transmission to electrode, find after deliberation, these special constructions are mainly made up of cytopigment, and its conductive capability is extremely strong, so be called as " nm-class conducting wire ".This " nm-class conducting wire " can be attached to electrode surface for a long time and grow and keep active, oxidation of organic compounds without while by electron transmission to electrode surface.
Cyanobacteria, Armatimonadetes, Deinococcus are wherein the electrochemical activity bacterium being active in negative electrode.They as electron acceptor(EA), accepting the electronics from negative electrode, and are utilized when micro-reduction material, ensure that the operation of apparatus of the present invention efficient stable.
Claims (10)
1. the auxiliary microbial augmentation degrading high concentration pharmacy wastewater treatment device of electricity, is characterized in that this device comprises water-in (1), water outlet (2), casing (3), top cover (4), water quality monitoring (WQM) mouth (5), poly (methyl methacrylate) plate (6), carbon fiber brush (8), titanium silk thread (9), effuser (7), wet test meter (10), water-sealed drainage bottle (11), deposition bucket (12) and mud discharging mouth (13), described casing (3) comprises eight compartments, is respectively the first compartment (3-1), second compartment (3-2), 3rd compartment (3-3), 4th compartment (3-4), 5th compartment (3-5), 6th compartment (3-6), 7th compartment (3-7) and the 8th compartment (3-8), separated by dividing plate between adjacent compartment, dividing plate lower end between first compartment (3-1) and the second compartment (3-2) is provided with a linked hole, dividing plate upper end between second compartment (3-2) and the 3rd compartment (3-3) is provided with a linked hole, dividing plate lower end between 3rd compartment (3-3) and the 4th compartment (3-4) is provided with a linked hole, dividing plate upper end between 4th compartment (3-4) and the 5th compartment (3-5) is provided with a linked hole, dividing plate lower end between 5th compartment (3-5) and the 6th compartment (3-6) is provided with a linked hole, dividing plate upper end between 6th compartment (3-6) and the 7th compartment (3-7) is provided with a linked hole, dividing plate lower end between 7th compartment (3-7) and the 8th compartment (3-8) is provided with a linked hole,
The upper end that the left side of described casing (3) is positioned at outside the first compartment (3-1) is provided with water-in (1), the upper end that the right side of casing (3) is positioned at outside the 8th compartment (3-8) is provided with water outlet (2), and casing (3) front side and rear side are positioned at outside each compartment and are equipped with water quality monitoring (WQM) mouth (5);
The top of each compartment is equipped with poly (methyl methacrylate) plate (6), the lower surface of each poly (methyl methacrylate) plate is all parallel is fixed with five carbon fiber brush groups (15), equidistantly on casing fore-and-aft direction in each carbon fiber brush group (15) be arranged with 4 carbon fiber brushes (8), the center of each carbon fiber brush (8) is provided with titanium silk thread (9), and titanium silk thread (9) is exposed to the upper surface of poly (methyl methacrylate) plate (6) through poly (methyl methacrylate) plate (6);
Three carbon fiber brush groups in five carbon fiber brush groups are as negative electrode, two carbon fiber brush groups are as anode, negative electrode and positive electrode is arrangement alternately, the titanium silk thread that each carbon fiber brush group as negative electrode is exposed to poly (methyl methacrylate) plate upper surface is all connected with the negative pole of transformer by wire, and the titanium silk thread that each carbon fiber brush group as anode is exposed to poly (methyl methacrylate) plate upper surface is all connected with the positive pole of transformer by wire;
Described casing (3) top is provided with top cover (4), distance is left between top cover (4) and poly (methyl methacrylate) plate (6), top cover (4) is provided with effuser (7), wet test meter (10) is connected by water-sealed drainage bottle (11) is airtight with effuser (7), the bottom of each compartment is equipped with deposition bucket (12), is equipped with mud discharging mouth (13) bottom each deposition bucket.
2. electricity according to claim 1 assists microbial augmentation degrading high concentration pharmacy wastewater treatment device, it is characterized in that the water quality monitoring (WQM) mouth outside each compartment is 2 ~ 4, is arranged at the upper and lower outside each compartment respectively, from top to bottom arranges in turn.
3. electricity according to claim 1 assists microbial augmentation degrading high concentration pharmacy wastewater treatment device, and it is characterized in that each carbon fiber brush (8) is in cylindric, diameter is 2 ~ 4cm.
4. electricity according to claim 1 assists microbial augmentation degrading high concentration pharmacy wastewater treatment device, it is characterized in that each carbon fiber brush group (15) is arranged in parallel on casing (3) left and right directions, dislocation arrangement between each carbon fiber brush group, make 3 of arbitrary neighborhood carbon fiber scopiforms become equilateral triangle, the distance between any two carbon fiber brushes is 4cm.
5. electricity according to claim 1 assists microbial augmentation degrading high concentration pharmacy wastewater treatment device, it is characterized in that the gap high vacuum silicone grease between described titanium silk thread (9) and poly (methyl methacrylate) plate (6) seals.
6. electricity according to claim 1 assists microbial augmentation degrading high concentration pharmacy wastewater treatment device, it is characterized in that the inclination angle of described deposition bucket (12) sidewall is 60 degree.
7. electricity according to claim 1 assists microbial augmentation degrading high concentration pharmacy wastewater treatment device, it is characterized in that the 4th compartment (3-4) and aspect ratio second compartment (3-2) of space bar upper end linked hole of the 5th compartment (3-5) and the low 5cm of height of the space bar upper end linked hole of the 3rd compartment (3-3), the 6th compartment (3-6) and the aspect ratio the 4th compartment (3-4) of space bar upper end linked hole of the 7th compartment (3-7) and the low 5cm of height of the space bar upper end linked hole of the 5th compartment (3-5).
8. utilize the electricity described in claim 1 to assist the method for microbial augmentation degrading high concentration pharmacy wastewater treatment device Pharmaceutical Wastewater Treatment, it is characterized in that the method, carry out according to the following steps:
One, pharmaceutical factory sewage works second pond returned sluge is crossed 10 eye mesh screens and remove macrobead thing, then in mud, add fresh pharmacy waste water, and add NaH
2pO
3and NH
4cl is in mud and pharmacy waste water mixture, the mass ratio of COD:N:P is made to be 200:5:1, continuous domestication two weeks, then put into by the mixture after domestication in each compartment of the auxiliary microbial augmentation degrading high concentration pharmacy wastewater treatment device of electricity, inoculum size is 2/3 of each compartment useful volume;
Two, titanium silk thread is connected with transformer, transformer voltage is 0.7 ~ 1.2V, temperature of reaction is 25 ~ 35 DEG C, pH value 6 ~ 8, first run under sequence batch (pattern, when electricity assists the electric current between microbial augmentation degrading high concentration pharmacy wastewater treatment device inner cathode and anode to be greater than 25mA, when external wet test meter has monitored obvious gas output simultaneously, now carbon fiber brush surface biofilm success, operation scheme is changed into continuum micromeehanics pattern, arranging hydraulic detention time is 8 ~ 12h, ensure that the flow velocity that in casing, each compartment current rises or declines is 1 ~ 1.5m/h, water outlet water outlet, namely water treatment procedure is completed.
9. the method for process medicine waste water according to claim 8, it is characterized in that in step one, sludge concentration is 4 ~ 6g/L, described sludge concentration refers to the concentration of living microorganism in mud.
10. the method for process medicine waste water according to claim 8, is characterized in that the COD value of fresh pharmacy waste water in step one is 2500 ~ 4000mg/L.
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